Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines

Autores
Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes.
Fil: Pieslinger, German Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Cadranel, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universitat Erlangen Nuremberg; Alemania
Fil: Baraldo Victorica, Luis Mario. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Materia
CYANIDE-BRIDGE
DFT CALCULATIONS
ELECTRON TRANSFER
RUTHENIUM POLYPYRIDINES
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/142361
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/142361
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium PolypyridinesPieslinger, German EduardoCadranel, AlejandroBaraldo Victorica, Luis MarioCYANIDE-BRIDGEDFT CALCULATIONSELECTRON TRANSFERRUTHENIUM POLYPYRIDINEShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes.Fil: Pieslinger, German Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Cadranel, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universitat Erlangen Nuremberg; AlemaniaFil: Baraldo Victorica, Luis Mario. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaSociedade Brasileira de Química2020-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/142361Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario; Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines; Sociedade Brasileira de Química; Journal of the Brazilian Chemical Society; 31; 11; 5-2020; 2360-23700103-50531678-4790CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.scielo.br/j/jbchs/a/5rr5sGdtV4ZwTs7GkC9DVKk/?lang=eninfo:eu-repo/semantics/altIdentifier/doi/10.21577/0103-5053.20200135info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:10:47Zoai:ri.conicet.gov.ar:11336/142361instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:10:48.247CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
title Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
spellingShingle Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
Pieslinger, German Eduardo
CYANIDE-BRIDGE
DFT CALCULATIONS
ELECTRON TRANSFER
RUTHENIUM POLYPYRIDINES
title_short Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
title_full Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
title_fullStr Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
title_full_unstemmed Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
title_sort Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
dc.creator.none.fl_str_mv Pieslinger, German Eduardo
Cadranel, Alejandro
Baraldo Victorica, Luis Mario
author Pieslinger, German Eduardo
author_facet Pieslinger, German Eduardo
Cadranel, Alejandro
Baraldo Victorica, Luis Mario
author_role author
author2 Cadranel, Alejandro
Baraldo Victorica, Luis Mario
author2_role author
author
dc.subject.none.fl_str_mv CYANIDE-BRIDGE
DFT CALCULATIONS
ELECTRON TRANSFER
RUTHENIUM POLYPYRIDINES
topic CYANIDE-BRIDGE
DFT CALCULATIONS
ELECTRON TRANSFER
RUTHENIUM POLYPYRIDINES
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes.
Fil: Pieslinger, German Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Cadranel, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universitat Erlangen Nuremberg; Alemania
Fil: Baraldo Victorica, Luis Mario. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
description This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes.
publishDate 2020
dc.date.none.fl_str_mv 2020-05
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/142361
Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario; Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines; Sociedade Brasileira de Química; Journal of the Brazilian Chemical Society; 31; 11; 5-2020; 2360-2370
0103-5053
1678-4790
CONICET Digital
CONICET
url http://hdl.handle.net/11336/142361
identifier_str_mv Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario; Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines; Sociedade Brasileira de Química; Journal of the Brazilian Chemical Society; 31; 11; 5-2020; 2360-2370
0103-5053
1678-4790
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.scielo.br/j/jbchs/a/5rr5sGdtV4ZwTs7GkC9DVKk/?lang=en
info:eu-repo/semantics/altIdentifier/doi/10.21577/0103-5053.20200135
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.069144

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